CN102405246B - Epoxy resins with improved flexural properties - Google Patents

Epoxy resins with improved flexural properties Download PDF

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CN102405246B
CN102405246B CN201080017181.9A CN201080017181A CN102405246B CN 102405246 B CN102405246 B CN 102405246B CN 201080017181 A CN201080017181 A CN 201080017181A CN 102405246 B CN102405246 B CN 102405246B
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epoxy resin
microns
particle
prepreg
resin
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CN102405246A (en
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王仰贤
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Hexcel Corp
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Hexcel Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

Epoxy resin compositions that include an epoxy resin component and a curative powder comprising particles of 4,4'-diaminobenzanilide (DABA) wherein the size of the DABA particles is less than 100 microns and wherein the median particle size is below 20 microns.

Description

There is the epoxy resin of the flexural properties of improvement
Technical field
The high-performance epoxy resin that relate generally to of the present invention uses in aerospace industry.More specifically, the present invention relates to improve flexural strength (flexural strength) and the breaking strain of this epoxy resin.
Background technology
In the occasion that much needs high structural strength and low weight, use with the epoxy resin that filamentary material is strengthened as glass or carbon fiber.Use the matrix material of high-performance epoxy resin matrix especially popular in aerospace industry, wherein weight and structural strength are important engineering and design considerations.High-performance epoxy resin can comprise the thermoplastic material that one or more provide " toughness reinforcing (toughening) " of epoxy resin.In addition, provide best solidifying and mechanical strength of resin with the combination of various solidifying agent.So although this high-performance epoxy resin composite material is because having relatively high intensity is desirable to weight ratio, there are some specific questions aspect flexible (flexibility) and flexural properties (flexural properties) in them.The flexural properties of epoxy resin is important for design is considered, because use bulk strength, damage tolerance and the shock-resistance of the composite part of this epoxy resin manufacture to depend on these character.
Flexural strength, modulus in flexure and breaking strain are the flexural properties of the cured epoxy resin of routine measurement in aerospace industry.The flexural strength of cured epoxy resin is defined as to the ability of resistance to distortion under load.Flexural strength is measured by the following method: measure the power of cured epoxy resin sample fracture needs or the amount of load of making.The material not breaking for remarkable distortion, crushing load is the point that the resistance to bend of sample sharply reduces.Modulus in flexure is the ratio of stress between cured epoxy resin deformation phases (load) to strain (deflection).Modulus in flexure is measured by the following method: use the value obtaining at flexural strength test period to calculate modulus in flexure.Measuring of breaking strain bending (strain) degree that was sample before fracture.
ASTM D790 and ISO 178 are two kinds of standard test procedures for measuring cured epoxy resin flexural properties.These two kinds of programs are basic identical.Sample support is being supported to span (support span) above and load (stress) is being applied to center by loading head (loading nose), thereby producing three-point bending (strain) with schedule speed.The various parameters of testing sequence comprise support span size, loading velocity and the maximum deflection of test.These parameters depend on specimen size, and they are different between ASTM D970 and ISO 178 codes.The Commonly Used Size of sample is 3.2mmx12.7mmx125mm (for ASTM D790 test) and 10mmx4mmx80mm (for ISO178 test).
In the industry of aerospace matrix material, development high-performance epoxy resin (wherein make flexural strength and breaking strain high as far as possible, and deleteriously do not affect modulus in flexure) has been and has continued to be major objective.
Epoxy resin formulation comprises one or more solidifying agent conventionally.A kind of this solidifying agent is 4, and 4 '-diaminobenzene formylaniline (4,4 '-diaminobenzanilide) (DABA).DABA provides usually used as powder, and itself and epoxy resin are directly mixed.The epoxy resin that it is desirable to provide curing with DABA and its present flexural strength and the breaking strain of improvement, and deleteriously do not affect the modulus in flexure of DABA-cured epoxy resin.
Summary of the invention
According to the present invention, find unexpectedly, can improve so flexural strength and the breaking strain of high-performance epoxy resin if used containing the powder of specific dimensions 4,4 '-diaminobenzene formylaniline (DABA) particle as solidifying agent.Also find, can realize these unforeseeable raisings of flexural strength and breaking strain, simultaneously compared with the existing high-performance epoxy resin that uses conventional solidifying agent to solidify, modulus in flexure quite or higher.In addition, cured resin of the present invention presents relatively high second-order transition temperature (T g).
Uncured composition epoxy resin is contained in the present invention, described composition comprises epoxy resin ingredient and by 4, the molecular solidifying agent powder of 4 '-diaminobenzene formylaniline (DABA) grain, described 4,4 '-diaminobenzene formylaniline (DABA) particle has and is less than the granularity of 100 microns and wherein said median particle lower than 20 microns.With to comparing with breaking strain level containing the flexural strength observed compared with the epoxy resin of the commercially available DABA powder curing of volume particle size, significantly higher by flexural strength and the breaking strain level of the epoxy resin of (specially sized) DABA solidifying agent powder curing of this specific dimensions.Also find that described cured resin has unforeseeable high glass-transition temperature.
Except uncured composition epoxy resin, the purposes of described composition epoxy resin as other combination of prepreg matrix resin and described uncured epoxy composite and filamentary material also contained in the present invention.In addition, Cured epoxy resin compositions and fibre reinforced composites parts are contained in the present invention, and wherein resinous substrates is according to Cured epoxy resin compositions of the present invention.The method and the method for preparation in conjunction with the hardening element of described composition epoxy resin of preparing uncured composition epoxy resin are also contained in the present invention.
With reference to following the detailed description and the accompanying drawings, will understand better above-mentioned and many further features of the present invention and follow advantage.
Brief description of the drawings
Fig. 1 is the figure that shows the size-grade distribution of the former state DABA solidifying agent powder of receiving from supplier.
Fig. 2 shows according to the figure of the size-grade distribution of DABA solidifying agent powder of the present invention.
Embodiment
Can in the occasion of cured epoxy resin much need to high flexural strength and breaking strain, use according to composition epoxy resin of the present invention.Described composition epoxy resin also can be used for needing the second-order transition temperature (T of cured resin g) higher than the occasions of 220 DEG C.Although described composition epoxy resin can be used alone, conventionally described composition and fiber support body are combined to form to matrix material.The form that described matrix material can be prepreg or solidifies final parts.Although described matrix material can be used for the purposes of any hope, they preferably in aerospace applications for structure and non-structure unit.
For example, the structure unit that described epoxy resin can be used for being formed on flyer is as the matrix material using in fuselage, wing and empennage.Described epoxy resin also can be used for being manufactured on the composite part using in the non-structural region of aircraft.Exemplary non-structural outer parts comprise nacelle and aircraft skin.Exemplary internal part comprises galley (galley) and lavatory (lavatory) structure, and containing box (overhead storage bins), partition wall (wall partitions), wardrobe, pipeline, ceiling panel (ceiling panels) and internal side wall on window frame, floor (floor panels), head.
The epoxy resin ingredient that comprises one or more epoxy resin that composition epoxy resin of the present invention comprises 55-75 % by weight.Any epoxy resin using in the optional comfortable high-performance aerospace epoxy resin of described epoxy resin.Can use two senses, trifunctional and tetrafunctional epoxy resin.Preferably, described epoxy resin ingredient will be made up of trifunctional epoxy compounds substantially.If wish, can comprise tetrafunctional epoxy resin.The relative quantity of trifunctional and tetrafunctional epoxy resin can change.But, preferably: trifunctional epoxy resin's amount is more than or equal to the amount of tetrafunctional epoxy resin.
Trifunctional epoxy resin is interpreted as to contraposition or a position on the phenyl ring in compound main chain have direct replacement or indirect three epoxide groups that replace.Tetrafunctional epoxy resin is interpreted as in compound main chain, have four epoxide groups.For example, applicable substituting group comprises hydrogen, hydroxyl, alkyl, thiazolinyl, alkynyl, alkoxyl group, aryl, aryloxy, aralkyl oxy, aralkyl, halogen, nitro or cyano group.Be applicable to non-epoxy substituting group can be combined in contraposition or the ortho position of phenyl ring, or be combined in do not occupied by epoxide group between position.
For example, applicable trifunctional epoxy resin comprises based on following those: phenol and cresols novolak (phenol and cresol epoxy novolacs); The glycidyl ether of phenolic adducts; Aromatic epoxy resin; Two aliphatic triglycidyl group ethers (dialiphatic triglycidyl ethers); The many glycidyl ethers of aliphatic series; Epoxidation of olefins; Brominated resins, aromatics glycidyl group amine and glycidyl ether; Heterocycle glycidyl imide and acid amides (heterocyclic glycidyl imidines and amides); Glycidyl ether; Fluorinated epoxy resin or its any combination.Preferred trifunctional epoxy resin is the triglycidyl group ether of p-aminophenol, and it can be used as Araldite MY 0500 or MY 0510 is purchased from HuntsmanAdvanced Materials (Monthey, Switzerland).Another preferred trifunctional epoxy resin is triglycidyl group Metha Amino Phenon.Particularly preferred trifunctional epoxy resin is triglycidyl group Metha Amino Phenon, it can be used as trade(brand)name Araldite MY0600 from Huntsman AdvancedMaterials (Monthey, Switzerland) be purchased, with be purchased from SumitomoChemical Co. (Osaka, Japan) as trade(brand)name ELM-120.
For example, applicable tetrafunctional epoxy resin comprises based on following those: phenol and cresols novolak; The glycidyl ether of phenolic adducts; Aromatic epoxy resin; Two aliphatic triglycidyl group ethers; The many glycidyl ethers of aliphatic series; Epoxidation of olefins; Brominated resins, aromatics glycidyl group amine and glycidyl ether; Heterocycle glycidyl imide and acid amides; Glycidyl ether; Fluorinated epoxy resin or its any combination.Preferred tetrafunctional epoxy resin is N, N, and N ', N '-four glycidyl group-m-xylenedimaine, it can be used as Araldite MY0720 or MY0721 is purchased from Huntsman AdvanceMaterials (Monthey, Switzerland).
If wished, described epoxy resin ingredient also can comprise difunctional epoxy resin, for example bisphenol-A (Bis-A) or bisphenol-f (Bis-F) epoxy resin.Exemplary Bis-A epoxy resin can be used as AralditeGY6010 (Huntsman Advanced Materials) and is purchased or can be used as DER 331 and be purchased from DowChemical Company (Midland, MI).Exemplary Bis-F epoxy resin can be used as AralditeGY281 and GY285 (Huntsman Advanced Materials) is purchased.The amount of the Bis-A existing in described epoxy resin ingredient or Bis-F epoxy resin can change.Preferably, the total epoxy component that is no more than 20 % by weight is difunctional epoxy resin.
Described epoxy resin ingredient can optionally comprise the thermoplastic toughening agent of 5-15 % by weight.For using preparing in high-performance epoxy resin, thermoplastic toughening agent is known.Exemplary toughner comprises polyethersulfone (PES), polyetherimide (PEI), polymeric amide (PA) and polyamidoimide (PAI).PES can be purchased from many chemical manufacturers.As an example, PES can be purchased as trade(brand)name Sumikaexcel 5003p from Sumitomo Chemical Co.Ltd. (Osaka, Japan).Polyetherimide can be used as ULTEM 1000P and is purchased from Sabic (Dubai).Polyamidoimide can be used as TORLON 4000TF and is purchased from SolvayAdvanced Polymers (Alpharetta, GA).Described thermoplastic component, preferably as powder supplies, mixed it before adding solidifying agent with described epoxy resin ingredient.
Described composition epoxy resin also can comprise other composition, and for example performance strengthens and/or changes agent, and condition is flexural strength, breaking strain and the modulus in flexure that they also can not adversely affect cured resin.Described performance strengthens and/or changes agent and for example can be selected from: tenderizer, granular filler, nanoparticle, shell/core rubber particles, fire retardant, wetting agent, pigment/dye, conductive particles (conducting particles) and viscosity-modifying agent.Preferably, described resin combination does not comprise other composition.Preferably, described resin combination only limit to epoxy component and specific dimensions solidifying agent powder, as described below.More preferably, described resin combination will comprise trifunctional epoxy resin and the solidifying agent powder as the specific dimensions of solidifying agent.The trifunctional epoxy resin that most preferably the DABA solidifying agent powder of specific dimensions and a position replace is as the combination of MY0600.
According to the present invention, use powdery 4,4 '-diaminobenzene formylaniline (DABA) solidifies described epoxy resin ingredient as solidifying agent.Powdery DABA solidifying agent is preparation by the following method preferably: adopt commercially available DABA powder and make it sieve (0.0015 inch of opening) by No.400.The size-grade distribution of the commercially available DABA powder of typical case is shown in Figure 1.This DABA powder can derive from many commercial source.Exemplary supplier comprises Acros Organics (Fair Lawn, NJ) and Alfa Aesar (Ward Hill, MA).Described powder is generally the pure DABA of at least 95 % by weight and is more typically the pure DABA of at least 98 % by weight.Use Horiba LA-500 particle-size analyzer to measure the size-grade distribution of business powder.Described " former state ' business powder packets is containing greatly to 200 microns and the little particle to 0.2 micron.Median particle is that approximately 48 microns and mean particle size are approximately 53 microns.The particle that approximately 38% particle has the granularity of 10-50 micron and approximately 14% has the granularity that exceedes 100 microns.Approximately 40% particle has the granularity of 50-100 micron.
In the time that above-mentioned business DABA powder sieves by No.400, the powder of the specific dimensions of gained has size distribution curve shown in figure 2, uses Horiba LA-500 particle size analyzer.There is flexural strength, breaking strain and T that the powdery DABA solidifying agent of the specific dimensions of the size-grade distribution shown in Fig. 2 provides glevel be significantly higher than to containing shown in Fig. 1 compared with the viewed flexural strength of epoxy resin, breaking strain and the T of the commercially available DABA powder curing of macroparticle glevel.
Should there is little particle (if any) that is greater than 100 microns according to the DABA powder of specific dimensions of the present invention.The powder of specific dimensions is also by the particle (if any) that contains little granularity and be less than approximately 0.1 micron.Smaller particle size is possible and can be included in the powder of specific dimensions.But routine is milled and material sieving technology does not produce the particle that is less than in a large number 0.1 micron conventionally.Therefore, under preferred granularity, be limited to approximately 0.1 micron.The median particle of powder should be lower than 20 microns.Preferably, median particle is 10-20 micron, and particularly preferred median particle is approximately 15 microns.The mean particle size of powder also should be lower than 20 microns.Preferably, mean particle size is 10-20 micron, and particularly preferred mean particle size is approximately 17 microns.At least 70% particle should have the granularity lower than 50 microns.Preferably approximately 85% particle has the granularity lower than 50 microns, and most preferably, at least 95% particle has the granularity lower than 50 microns.Further preferably, there is at least about 16% particle the granularity that is less than 5 microns.
The DABA powder of specific dimensions can be made by a lot of modes, and condition is to obtain above-mentioned size-grade distribution.For example, the DABA of relative bulk can be pulverized and passes through various sieves, to obtain the size-grade distribution similar to commercially available powder shown in Fig. 1.Then make gained powder sieve to obtain the molecular powder of grain by meeting above-mentioned particle size distribution by No.400.Preferably, buy or prepare the powder having with the same or analogous size-grade distribution of size-grade distribution shown in Fig. 1, then making it sieve to obtain the DABA powder of specific dimensions by No.400.If wish, the powder that is purchased with size-grade distribution shown in Fig. 1 further can be pulverized before sieving by No.400.The DABA powder of described specific dimensions should be the DABA of at least 95 % by weight.More preferably, described powder should be the pure DABA of at least 98 % by weight.
Can change the amount of the DABA solidifying agent powder that mixes the specific dimensions that forms uncured composition epoxy resin with described epoxy resin ingredient, to provide flexural strength as at least 25ksi and the breaking strain value cured resin as at least 4%, use ASTM D970 to measure.Modulus in flexure should be about 790ksi or higher and T gshould be 220 DEG C or higher.Preferably, epoxy component is 1.0: 1.0 to 1.0: 0.6 to the stoichiometric ratio of DABA.Epoxy component is approximately 1.0: 0.85 to the preferred stoichiometric ratio of DABA.In described composition epoxy resin, can comprise other a small amount of solidifying agent.But, preferably, the DABA solidifying agent powder that the epoxy resin ingredient solidifying agent of at least 80 % by weight is specific dimensions.Most preferably so uncured composition epoxy resin: wherein said solidifying agent is the DABA solidifying agent powder of the specific dimensions of at least 95 % by weight.Addible exemplary other solidifying agent comprises 3,3 '-diaminodiphenylsulfone(DDS) (3,3 '-DDS) and 4,4′ diaminodiphenyl sulfone (4,4 '-DDS).
Composition epoxy resin of the present invention is according to the normal resin work program preparation for high-performance epoxy resin.Exceed a kind of epoxy resin if used, so by described epoxy resin in mixed at room temperature together to form epoxy resin ingredient.Add any thermoplastic component or other additive, then heated mixt (if necessary), with solution heat plasticity or other additive.Then by cooling mixture (if necessary) to 65 DEG C or lesser temps (preferably room temperature), and the DABA solidifying agent powder of specific dimensions is mixed in resin compound, to form final uncured composition epoxy resin.Should be by DABA solidifying agent powder dissolution before being added into described epoxy resin ingredient.As shown in comparative example 3, in the time using the DABA powder of specific dimensions as solidifying agent, predissolve DABA powder in solvent (as the replacement scheme that reduces powder size) does not provide the flexural properties of improvement.
Uncured composition epoxy resin can be used for needing in any application of high-performance epoxy resin.But the basic purposes of this resin is and fortifying fibre (fibrous reinforcement) combines, and forms prepreg, described prepreg is used to form cured composite material parts later.Described uncured composition epoxy resin is applied to fortifying fibre according to any known prepreg manufacturing technology.During forming prepreg, available described composition epoxy resin completely or partially floods fortifying fibre.Conventionally prepreg is covered with protective membrane and is rolled on two sides and store and transport, conventionally keep temperature fully lower than room temperature to avoid premature curing.If desired, can use any other prepreg manufacture method and storage/transport system.
Compound or the blend fiber system of described fortifying fibre optional self-contained synthetic or natural fiber or its combination.Exemplary preferred reinforcing fiber materials comprises glass fibre, carbon fiber or aromatic poly amide (aramid) (aromatic poly amide (aromatic polyamide)) fiber.Fortifying fibre preferably comprises carbon fiber.
Described fortifying fibre can comprise cracking (that is, breaking) or selectivity discontinuous fibre, or continuous fibre.Described fortifying fibre can be and weaves, non-crimping (non-crimped), non-woven, unidirectional or multiaxis woven fabric structure form, the quasi-isotropic cut off machine (quasi-isotropic chopped pieces ofunidirectional fibers) of for example unidirectional fibre.Weaving form is optional from plain weave, satin weave or twill type.Non-crimping and multiaxis form can have many plying (plies) and fibre orientation.This type and form are known in composite material reinforcement body field, and can be purchased from many companies, comprise Hexcel Reinforcements (Villeurbanne, France).
Described prepreg can be the form of continuous band, powder coated fibrous bundle, reticulation or cutting length (chopped lengths) (cutting off and cut off operation after described composition epoxy resin immerses in fortifying fibre can carry out at any point).Described prepreg can be used as viscosity or veneer film and also can have the embedding carrier of various forms (woven, knitting and non-woven form).
Can use any molded prepreg of standard technique that is used to form composite part.Typically, the one or more of prepreg are placed in applicable mould and are solidified to form final composite part.Can use any applicable temperature known in the art, pressure and time conditions completely or partially to solidify containing the prepreg of the uncured composition epoxy resin of the present invention.Typically, prepreg in autoclave with the temperature-curable of 160 DEG C-190 DEG C, the preferably solidification value of approximately 175 DEG C-185 DEG C.The prepreg of quasi-isotropic cut-out or the compression molding of moulding material are preferred programs.The prepreg of described quasi-isotropic cut-out with can derive from Hexcel Corporation's (Dublin, CA) compression molding material is identical, and the resin Composition of the prepreg of this quasi-isotropic cut-out that different is is produced according to the present invention.This quasi-isotropic material is described in EP 113431B1 and U.S. Patent application 11/476,965.
Put into practice embodiment as follows:
comparative example 1
Prepare relatively epoxy resin samples, wherein by 20.00g MY600 (triglycidyl group Metha Amino Phenon) epoxy resin and 9.14g 3,3 '-DDS and 1.02g 4,4 '-DDS mixes, and it is the conventional solidifying agent for solidifying high-performance epoxy resin.Epoxy resin is solidified to 2 hour to form cured resin sample at 177 DEG C with solidifying agent together with mixed at room temperature and by gained resin, according to ASTM D790 test sample.The modulus in flexure of cured resin sample is 749ksi.Flexural strength is that 31.1ksi and breaking strain are 4.0%.The T of cured resin git is 205 DEG C.
comparative example 2
Prepared relatively epoxy resin samples, wherein 21.20g MY600 epoxy resin has been mixed with 9.86gDABA solidifying agent powder (deriving from supplier's former state), it provides the MY600 of 1: 0.85: DABA stoichiometric ratio.The size-grade distribution of DABA solidifying agent powder is shown in Figure 1.The median particle of powder is that approximately 48 microns and mean particle size are approximately 53 microns.Approximately 14% particle has the granularity of 100-200 micron and approximately 8% and has the granularity that is less than 15 microns.Approximately 70% particle has the granularity of 150 microns-30 microns.
Epoxy resin is solidified to 2 hour to form cured resin sample at 177 DEG C with DABA solidifying agent powder together with mixed at room temperature and by gained resin, according to ASTM D790 test sample.The modulus in flexure of cured resin sample is 745ksi.Flexural strength is that 12.2ksi and breaking strain are 2.4%.The T of cured resin sample git is 214 DEG C.
comparative example 3
By MY600 epoxy resin is mixed from the DABA solidifying agent of different amounts, prepare three kinds of relatively epoxy resin samples (CA, CB and CC).Epoxy resin as described in DABA solidifying agent powder not being added directly to as in comparative example 2, but powder was dissolved in dioxolane before being added into resin.Resin CA contains 17.92g MY600 and 10.11g DABA, and it provides the MY600 of 1: 1: DABA stoichiometric ratio.Resin CB contains 21.20g MY600 and 9.86gDABA (stoichiometric ratio of 1: 0.85).Resin CC contains 21.75g MY600 and 8.82gDABA (stoichiometric ratio of 1: 0.75).
By the DABA powder of epoxy resin and dissolving together with mixed at room temperature to form three kinds of relatively mixtures.Mixture is heated to 50 DEG C and keep approximately 2 hours in this temperature from room temperature under 30 inches of Hg, with evaporating solvent.Gained resin (CA, CB and CC) is solidified to 2 hours to form curing ratio compared with resin sample at 177 DEG C, according to ASTM D790 test sample.The modulus in flexure of cured resin sample is: 825ksi (resin CA); 863ksi (resin CB); And 816ksi (resin CC).Flexural strength is: 13.9ksi (resin CA); 17.4ksi (resin CB); And 19.2ksi (resin CC).Breaking strain is: 1.7% (resin CA); 2.0% (resin CB); With 2.4% (resin CC).The T of cured resin gbe respectively 202 DEG C, 219 DEG C and 199 DEG C for resin CA, CB and CC.
embodiment 1
By MY600 epoxy resin is mixed from the DABA solidifying agent powder of different amounts, prepare three kinds of exemplary epoxy resin samples (A, B and C).Epoxy resin as described in DABA solidifying agent powder not being added directly to as in comparative example 2, but by powder first by 400 mesh screens so that size-grade distribution powder to be as shown in Figure 2 provided.The median particle of powder is that approximately 15 microns and mean particle size are approximately 16 microns.There is no granularity higher than approximately 100 microns and do not have particle to have to be less than the granularity of 0.1 micron.The particle that approximately 3% particle has the granularity of 50-100 micron and approximately 25% has the granularity that is less than 10 microns.Approximately 75% particle has the granularity of 50 microns-10 microns.
The DABA that Resin A contains 17.92g MY600 and the reduction of 10.11g granularity, it provides the stoichiometric ratio of the MY600 of 1: 1: DABA.The DABA (stoichiometric ratio of 1: 0.85) that resin B contains 21.20g MY600 and the reduction of 9.86g granularity.The DABA (stoichiometric ratio of 1: 0.75) that resin C contains 21.75g MY600 and the reduction of 8.82g granularity.
The DABA powder that described epoxy resin and granularity are reduced together with mixed at room temperature to form three kinds of exemplary resin sample A, B and C.Gained resin is solidified to 2 hours to form cured resin sample at 177 DEG C, according to ASTM D790 test sample.The modulus in flexure of cured resin sample is: 794ksi (Resin A); 794ksi (resin B); And 801ksi (resin C).Flexural strength is: 27.7ksi (Resin A); 33.6ksi (resin B); And 30.2ksi (resin C).Breaking strain is: 4.6% (Resin A); 5.6% (resin B); With 4.9% (resin C).The T of cured resin gbe respectively 229 DEG C, 234 DEG C and 227 DEG C for Resin A, B and C.
Can find out from example above, compare with 3 with comparative example 2, the flexural strength of embodiment 1 and breaking strain are significantly with against expectation higher.According to applicant's invention, have been found that, the flexural strength that the epoxy resin of the DABA solidifying agent powder curing reducing by the granularity of embodiment 1 is realized and breaking strain level can not be used compared with the smaller particle size particle shown in volume particle size DABA particle (comparative example 2) or comparative example 3 (, the DABA powder of dissolving) and realize.Also remain on higher level according to the present invention by the modulus in flexure of the curing resin of the DABA of granularity reduction.In addition, the T of exemplary resin gagainst expectation higher than the T that compares resin g.
The curing epoxy resin of the conventional solidifying agent of use (3,3 '-DDS and 4,4 '-DDS) according to the present invention shown in the flexural strength of the resin of (A, B and C) and breaking strain level and comparative example 1 is in same range.The modulus in flexure of the compared epoxy resin that in addition, the modulus in flexure of DABA cured resin of the present invention is solidified with the conventional solidifying agent of use of setting forth in comparative example 1 is equally high or higher.
Although described exemplary of the present invention, those skilled in the art it should be noted, the content wherein disclosing is only exemplary, and can carry out within the scope of the present invention various other possibilities, change and improvement.Therefore, the present invention is not limited by above-mentioned embodiment, limited by claims.

Claims (12)

1. prepreg, it comprises
Uncured composition epoxy resin, described uncured composition epoxy resin comprises epoxy resin ingredient, with comprise 4, the solidifying agent powder of 4 '-diaminobenzene formylaniline particle, the granularity of wherein said particle is less than the median particle of 100 microns and wherein said particle lower than 20 microns; And
Fiber support structure;
Wherein said epoxy resin ingredient is made up of trifunctional epoxy resin substantially, and described epoxy resin ingredient is to described 4, and the stoichiometric ratio of 4'-diaminobenzene formylaniline is 1.0:1.0 to 1.0:0.7.
2. the prepreg of claim 1, wherein said median particle be 10 microns to lower than 20 microns.
3. the prepreg of claim 1, wherein said epoxy resin ingredient is to described 4, and the stoichiometric ratio of 4'-diaminobenzene formylaniline is 1.0:0.85.
4. the prepreg of claim 1, wherein in described solidifying agent powder, at least 70% particle has the granularity lower than 50 microns.
5. curing composite part, it comprises the prepreg of curing claim 1.
6. the curing composite part of claim 5, wherein uncured composition epoxy resin has at least flexural strength of 25ksi and at least 4.0% breaking strain after solidifying.
7. the method for preparing prepreg, it comprises the following steps:
Uncured composition epoxy resin is provided, and it comprises that median particle that epoxy resin ingredient and comprise 4, the solidifying agent powder of 4 '-diaminobenzene formylaniline particle, the granularity of wherein said particle be less than 100 microns and wherein said particle is lower than 20 microns;
By uncured composition epoxy resin and fiber support structure combination, thereby form described prepreg;
Wherein said epoxy resin ingredient is made up of trifunctional epoxy resin substantially, and described epoxy resin ingredient is to described 4, and the stoichiometric ratio of 4'-diaminobenzene formylaniline is 1.0:1.0 to 1.0:0.7.
8. the method for preparing prepreg of claim 7, wherein said median particle be 10 microns to lower than 20 microns.
9. the method for preparing prepreg of claim 7, wherein said epoxy resin ingredient is to described 4, and the stoichiometric ratio of 4'-diaminobenzene formylaniline is 1.0:0.85.
10. the method for preparing prepreg of claim 7, wherein in described solidifying agent powder, at least 70% particle has the granularity lower than 50 microns.
11. prepare the method for curing composite part, said method comprising the steps of: the prepreg of claim 1 is provided, and solidifies described prepreg, form curing composite part.
The method of the curing composite part of the preparation of 12. claims 11, wherein uncured composition epoxy resin has at least flexural strength of 25ksi and at least 4.0% breaking strain after solidifying.
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